KR102612264B1 - Inorganic binder and liquid-phase polymer composition - Google Patents

Inorganic binder and liquid-phase polymer composition Download PDF

Info

Publication number
KR102612264B1
KR102612264B1 KR1020220183328A KR20220183328A KR102612264B1 KR 102612264 B1 KR102612264 B1 KR 102612264B1 KR 1020220183328 A KR1020220183328 A KR 1020220183328A KR 20220183328 A KR20220183328 A KR 20220183328A KR 102612264 B1 KR102612264 B1 KR 102612264B1
Authority
KR
South Korea
Prior art keywords
weight
calcium
inorganic binder
parts
cement
Prior art date
Application number
KR1020220183328A
Other languages
Korean (ko)
Inventor
박정준
홍표
이대근
Original Assignee
주식회사 정우소재
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 정우소재 filed Critical 주식회사 정우소재
Priority to KR1020220183328A priority Critical patent/KR102612264B1/en
Application granted granted Critical
Publication of KR102612264B1 publication Critical patent/KR102612264B1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
    • C04B28/186Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
    • C04B28/188Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00Calcium sulfate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/26Carbonates
    • C04B14/28Carbonates of calcium
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/30Oxides other than silica
    • C04B14/305Titanium oxide, e.g. titanates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04Carboxylic acids; Salts, anhydrides or esters thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/06Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2623Polyvinylalcohols; Polyvinylacetates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641Polyacrylates; Polymethacrylates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2676Polystyrenes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/32Aluminous cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/32Aluminous cements
    • C04B7/323Calcium aluminosulfate cements, e.g. cements hydrating into ettringite

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

본 발명은 칼슘-실리케이트 시멘트 (CSC : Calcium Silicate Cement) 20~80 중량%; C12A7계 칼슘-알루미네이트 시멘트 (CAC : Calcium Aluminate Cement) 9~40 중량%; 황산칼슘 (CS : Calcium Sulfate) 10~40 중량%;를 포함하는 것을 특징으로 하는 무기질 결합재 및 이를 이용한 액상 폴리머 조성물을 제시함으로써, 초기 물성 발현이 가능하고, CSC 시멘트와 공기 중 이산화탄소 반응에 의한 장기적인 조직 치밀성 및 내구성이 개선되며, 특히 해안가 구조물의 보호 및 보수에 효과적으로 적용할 수 있도록 한다.The present invention provides calcium-silicate cement (CSC) of 20 to 80% by weight; C 12 A 7 series calcium-aluminate cement (CAC: Calcium Aluminate Cement) 9 to 40% by weight; By presenting an inorganic binder characterized by containing 10 to 40% by weight of calcium sulfate (CS: Calcium Sulfate) and a liquid polymer composition using the same, it is possible to develop initial physical properties and achieve long-term stability through the reaction between CSC cement and carbon dioxide in the air. Tissue density and durability are improved, and it can be especially effectively applied to the protection and repair of coastal structures.

Description

무기질 결합재 및 이를 이용한 액상 폴리머 조성물{INORGANIC BINDER AND LIQUID-PHASE POLYMER COMPOSITION}Inorganic binder and liquid polymer composition using the same {INORGANIC BINDER AND LIQUID-PHASE POLYMER COMPOSITION}

본 발명은 건설 재료분야에 관한 것으로서, 상세하게는 무기질 결합재 및 이를 이용한 액상 폴리머 조성물에 관한 것이다.The present invention relates to the field of construction materials, and more specifically to inorganic binders and liquid polymer compositions using the same.

현재 세계는 지구온난화에 대한 대처 방안으로서, 이산화탄소 감축이 가장 중요한 방안으로 추진되고 있다.Currently, the world is promoting carbon dioxide reduction as the most important measure to combat global warming.

이에 시멘트 산업의 경우도 기존 시멘트 대비 이산화탄소 발생량을 최대 70% 까지 감축시킬 수 있는 이산화탄소 반응경화형 시멘트인 칼슘-실리케이트 시멘트 클링커(CSC)(특허공개 10-2022-0097663) 등을 개발하여 대처해 나가고 있으며, 이의 활용방안에 대한 연구도 활발히 진행 중에 있다.Accordingly, the cement industry is responding by developing calcium-silicate cement clinker (CSC), a carbon dioxide reaction hardening type cement that can reduce carbon dioxide emissions by up to 70% compared to existing cement (Patent Publication No. 10-2022-0097663). , research on how to utilize it is also actively underway.

CSC 시멘트는 반응 시 이산화탄소를 필요로 하기 때문에, 양생기 내에 이산화탄소 분위기 조건을 쉽게 만들 수 있는 벽돌, 블록, 프리캐스팅 콘크리드와 같은 공장생산 제품에 대하여 용이하게 적용할 수 있는 장점이 있다.Since CSC cement requires carbon dioxide for reaction, it has the advantage of being easily applied to factory-produced products such as bricks, blocks, and precast concrete that can easily create carbon dioxide atmosphere conditions within the curing period.

이에 반해, 기존 시멘트에 비해 초기 강도발현에 필요한 C3S 및 C2S 함량이 적고 CO2와 반응하는 CS 및 C3S2의 함량이 높은 CSC 시멘트의 경우 현장 타설제품에 적용하기 어렵다는 문제점이 있다. On the other hand, in the case of CSC cement, which has a lower content of C 3 S and C 2 S required for initial strength development compared to existing cement and a high content of CS and C 3 S 2 that react with CO 2 , the problem is that it is difficult to apply to cast-in-place products. there is.

따라서 속경성 시멘트를 CSC 시멘트와 같이 사용함으로써, 초기 강도를 확보하고 장기적으로 공기 중의 이산화탄소와 반응하는 조성물에 관한 연구가 필요한 실정이다. Therefore, by using fast-hardening cement together with CSC cement, research is needed on compositions that secure initial strength and react with carbon dioxide in the air in the long term.

한국공개특허 제10-2022-0097663호Korean Patent Publication No. 10-2022-0097663 일본등록특허 제5059285호Japanese Patent No. 5059285 일본공개특허 제2022-44570호Japanese Patent Publication No. 2022-44570 일본공개특허 제2021-175701호Japanese Patent Publication No. 2021-175701 일본공개특허 제2009-526198호Japanese Patent Publication No. 2009-526198 일본공개특허 제2021-187721호Japanese Patent Publication No. 2021-187721

본 발명은 상기와 같은 문제점을 해결하기 위하여 도출된 것으로서, 초기 물성 발현이 가능하고, CSC 시멘트와 공기 중 이산화탄소 반응에 의한 장기적인 조직 치밀성 및 내구성이 개선되며, 특히 해안가 구조물의 보호 및 보수에 효과적으로 적용할 수 있는 무기질 결합재 및 이를 이용한 액상 폴리머 조성물을 제시하는 것을 그 목적으로 한다.The present invention was developed to solve the above problems. It enables initial physical properties, improves long-term tissue density and durability due to the reaction of CSC cement with carbon dioxide in the air, and is particularly effective in protecting and repairing coastal structures. The purpose is to present an inorganic binder that can be used and a liquid polymer composition using the same.

상기 과제의 해결을 위하여, 본 발명은 칼슘-실리케이트 시멘트 (CSC : Calcium Silicate Cement) 20~80 중량%; C12A7계 칼슘-알루미네이트 시멘트 (CAC : Calcium Aluminate Cement) 9~40 중량%; 황산칼슘 (CS : Calcium Sulfate) 10~40 중량%;를 포함하는 것을 특징으로 하는 무기질 결합재를 제시한다.In order to solve the above problem, the present invention includes 20 to 80% by weight of calcium-silicate cement (CSC); C 12 A 7 series calcium-aluminate cement (CAC: Calcium Aluminate Cement) 9 to 40% by weight; An inorganic binder is presented, characterized in that it contains 10 to 40% by weight of calcium sulfate (CS: Calcium Sulfate).

칼슘-설퍼-알루미네이트 시멘트 (CSA : Calcium Sulfoaluminate) 0.1~20 중량%;를 더 포함하는 것이 바람직하다.It is preferable to further include 0.1 to 20% by weight of calcium-sulfur-aluminate cement (CSA).

상기 무기질 결합재 100 중량부를 기준으로, 개미산리튬 (Lithium formate), 염화리튬(Lithium chloride), 탄산리튬(Lithium Carbonate), 리튬염(Lithium Salt), 아질산칼슘(Calcium Nitrite), 개미산아민(Amine Formate) 중 하나 또는 2 이상의 혼합에 의한 촉진제 0.1~1.0 중량부; 글루콘산소다(Sodium Glucoante), 주석산 (Tartaric acid), 구연산 (Citric acid), 인산알루미늄(Aluminium Phosphate), 아세트산구리(Copper Acetate), 황산아연(Zinc Sulfate) 중 하나 또는 2 이상의 혼합에 의한 지연제 0.2~2.0 중량부;를 더 포함하는 것이 바람직하다.Based on 100 parts by weight of the inorganic binder, lithium formate, lithium chloride, lithium carbonate, lithium salt, calcium nitrite, and amine formate. 0.1 to 1.0 parts by weight of an accelerator by one or a mixture of two or more; Delay caused by one or a mixture of two or more of Sodium Glucoante, Tartaric acid, Citric acid, Aluminum Phosphate, Copper Acetate, and Zinc Sulfate. It is preferable to further include 0.2 to 2.0 parts by weight.

본 발명은 상기 무기질 결합재 20~50 중량%; 유동화제, 증점제, 소포제의 혼합에 의한 작업성 혼화제 0.3~1.5 중량%; 안료 49~79 중량%;를 포함하는 것을 특징으로 하는 분체 조성물을 제시한다.The present invention is 20 to 50% by weight of the inorganic binder; 0.3 to 1.5% by weight of workability admixture by mixing a fluidizer, thickener, and anti-foaming agent; A powder composition comprising 49 to 79% by weight of pigment is presented.

상기 작업성 혼화제는, 나프탈렌계, 멜라민계 또는 폴리카르본산계인 상기 유동화제 0.1~0.5 중량%; 스타치계 또는 셀룰로오즈계인 상기 증점제 0.1~0.5 중량%; 글리콜계 또는 실리콘계인 상기 소포제 0.1~0.5 중량%;를 포함하는 것이 바람직하다.The workability admixture includes 0.1 to 0.5% by weight of a naphthalene-based, melamine-based or polycarboxylic acid-based fluidizing agent; 0.1 to 0.5% by weight of the starch-based or cellulose-based thickener; It is preferable to include 0.1 to 0.5% by weight of the antifoaming agent, which is glycol-based or silicone-based.

상기 안료는, 석회석 분말, 중정석 분말, 티타늄화이트 (TiO2) 중 하나 또는 2 이상의 혼합에 의한 백색안료 48.9~69 중량%; 유색안료 0.1~10 중량 %;를 포함하는 것이 바람직하다.The pigment is 48.9 to 69% by weight of white pigment obtained by mixing one or more of limestone powder, barite powder, and titanium white (TiO2); It is preferable to include 0.1 to 10% by weight of colored pigment.

본 발명은 상기 분체 조성물 100 중량부; 유기 폴리머 5~20 중량부; 물 15~35 중량부;를 포함하는 것을 특징으로 하는 액상 폴리머 조성물을 제시한다.The present invention is 100 parts by weight of the powder composition; 5 to 20 parts by weight of organic polymer; A liquid polymer composition comprising 15 to 35 parts by weight of water is presented.

상기 유기 폴리머는, 아크릴계, 스타이렌-아크릴계, 비닐아세테이트 에틸렌(VAE)계, 폴리비닐 아세테이트(PVA)계, 스타이렌-부타디엔 수지(SBR)계 폴리머 중 하나 또는 2 이상의 혼합에 의해 형성된 것이 바람직하다.The organic polymer is preferably formed by one or a mixture of two or more of acrylic-based, styrene-acrylic-based, vinyl acetate ethylene (VAE)-based, polyvinyl acetate (PVA)-based, and styrene-butadiene resin (SBR)-based polymers. .

본 발명은 초기 물성 발현이 가능하고, CSC 시멘트와 공기 중 이산화탄소 반응에 의한 장기적인 조직 치밀성 및 내구성이 개선되며, 특히 해안가 구조물의 보호 및 보수에 효과적으로 적용할 수 있는 무기질 결합재 및 이를 이용한 액상 폴리머 조성물을 제시한다.The present invention provides an inorganic binder that can develop initial physical properties, improves long-term tissue density and durability due to the reaction of CSC cement with carbon dioxide in the air, and can be effectively applied in particular to the protection and repair of coastal structures, and a liquid polymer composition using the same. present.

이산화탄소 반응 시멘트인 CSC 시멘트의 활용분야를 넓힘으로써, 지구온난화 해결노력에 부합하고, 추후 다양한 현장타설용 몰탈 및 콘크리트로의 확대적용이 가능할 것으로 기대된다. By expanding the field of use of CSC cement, a carbon dioxide-reactive cement, it is expected that it will meet efforts to solve global warming and that expanded application to various cast-in-place mortars and concrete will be possible in the future.

이하, 본 발명의 실시예에 관하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.

본 발명에 의한 무기질 결합재는, 칼슘-실리케이트 시멘트 (CSC : Calcium Silicate Cement) 20~80 중량%; C12A7계 칼슘-알루미네이트 시멘트 (CAC : Calcium Aluminate Cement) 9~40 중량%; 황산칼슘 (CS : Calcium Sulfate) 10~40 중량%; 칼슘-설퍼-알루미네이트 시멘트 (CSA : Calcium Sulfoaluminate) 0.1~20 중량%;를 포함하여 구성된다.The inorganic binder according to the present invention contains 20 to 80% by weight of calcium-silicate cement (CSC); C 12 A 7 series calcium-aluminate cement (CAC: Calcium Aluminate Cement) 9 to 40% by weight; Calcium sulfate (CS: Calcium Sulfate) 10-40% by weight; It consists of 0.1 to 20% by weight of calcium-sulfur-aluminate cement (CSA).

CSC의 함량이 80 중량%를 초과하면 초기의 강도발현 특성이 부족하고, 20 중량% 미만으로 하면 장기적인 이산화탄소 반응에 대한 효과가 미미하다. If the CSC content exceeds 80% by weight, the initial strength development characteristics are insufficient, and if the CSC content is less than 20% by weight, the effect on the long-term carbon dioxide reaction is minimal.

위 무기질 결합재의 반응에 참여하는 기능성 혼화제로서, 무기질 결합재 100 중량부를 기준으로, 개미산리튬 (Lithium formate), 염화리튬(Lithium chloride), 탄산리튬(Lithium Carbonate), 리튬염(Lithium Salt), 아질산칼슘(Calcium Nitrite), 개미산아민(Amine Formate) 중 하나 또는 2 이상의 혼합에 의한 촉진제 0.1~1.0 중량부; 글루콘산소다(Sodium Glucoante), 주석산 (Tartaric acid), 구연산 (Citric acid), 인산알루미늄(Aluminium Phosphate), 아세트산구리(Copper Acetate), 황산아연(Zinc Sulfate) 중 하나 또는 2 이상의 혼합에 의한 지연제 0.2~2.0 중량부;를 더 포함하여 구성될 수 있다.As a functional admixture that participates in the reaction of the above inorganic binder, based on 100 parts by weight of the inorganic binder, lithium formate, lithium chloride, lithium carbonate, lithium salt, calcium nitrite 0.1 to 1.0 parts by weight of an accelerator made of one or a mixture of two or more of (Calcium Nitrite) and formic acid amine (Amine Formate); Delay caused by one or a mixture of two or more of Sodium Glucoante, Tartaric acid, Citric acid, Aluminum Phosphate, Copper Acetate, and Zinc Sulfate. It may further include 0.2 to 2.0 parts by weight.

촉진제는 상기 범위 미만의 경우 초기특성 발현이 미미하고, 상기범위 초과 시 효과대비 과도한 비용이 발생하여 비경제적이다. If the accelerator is below the above range, the development of initial characteristics is minimal, and if the accelerator exceeds the above range, excessive costs are incurred compared to the effect, making it uneconomical.

지연제는 상기 범위 미만의 경우 적정 작업시간 확보가 어렵고, 상기 범위를 초과할 경우 과도한 반응지연으로 초기의 물성확보에 어려움이 있다. If the retardant is below the above range, it is difficult to secure an appropriate working time, and if it exceeds the above range, it is difficult to secure initial physical properties due to excessive reaction delay.

본 발명에 의한 분체 조성물은, 위 무기질 결합재 20~50 중량%; 유동화제, 증점제, 소포제의 혼합에 의한 작업성 혼화제 0.3~1.5 중량%; 안료 49~79 중량%;를 포함하여 구성된다.The powder composition according to the present invention contains 20 to 50% by weight of the above inorganic binder; 0.3 to 1.5% by weight of workability admixture by mixing a fluidizer, thickener, and anti-foaming agent; Contains 49 to 79% by weight of pigment.

무기질 결합재의 경우, 20 중량% 이내에서는 코팅재의 표면경도가 약하고, 50 중량%를 초과하면 표면 균열의 위험성이 증대된다. In the case of an inorganic binder, the surface hardness of the coating material is weak within 20% by weight, and if it exceeds 50% by weight, the risk of surface cracking increases.

위 작업성 혼화제는 코팅재의 적정 평활성을 유지하기 위한 것으로서, 나프탈렌계, 멜라민계 또는 폴리카르본산계인 유동화제 0.1~0.5 중량%; 스타치계 또는 셀룰로오즈계인 증점제 0.1~0.5 중량%; 글리콜계 또는 실리콘계인 상기 소포제 0.1~0.5 중량%;를 포함하여 구성된다.The above workability admixture is to maintain the appropriate smoothness of the coating material, and includes 0.1 to 0.5% by weight of a naphthalene-based, melamine-based or polycarboxylic acid-based fluidizer; 0.1 to 0.5% by weight of a starch-based or cellulose-based thickener; It includes 0.1 to 0.5% by weight of the antifoaming agent, which is glycol-based or silicone-based.

유동화제 및 증점제는 작업성에 관여하고, 소포제는 코팅 표면의 기포발생을 억제한다. Fluidizers and thickeners are involved in workability, and antifoam agents suppress the generation of bubbles on the coating surface.

유동화제의 경우 상기 범위 미만에서는 적정 평활성을 확보하기가 어렵고, 상기 범위를 초과할 경우 재료분리 발생의 문제점이 발생한다. In the case of a fluidizing agent, if it is below the above range, it is difficult to secure appropriate smoothness, and if it is above the above range, problems of material separation occur.

증점제의 경우 상기 범위 미만에서는 적정 점도를 유지하기가 어렵고, 상기 범위를 초과하면 적정 평활성 확보가 어려워진다. In the case of a thickener, if it is below the above range, it is difficult to maintain an appropriate viscosity, and if it exceeds the above range, it is difficult to secure appropriate smoothness.

소포제의 경우 상기 범위 미만이면 코팅재 표면에 핀홀이 발생하여 미려한 표면을 발현하기 어렵고, 상기범위를 초과하면 효과대비 비용발생이 커 비경제적이다. In the case of an antifoaming agent, if it is less than the above range, pinholes will be generated on the surface of the coating material, making it difficult to create a beautiful surface, and if it is more than the above range, the cost will be high compared to the effectiveness, making it uneconomical.

안료는 도포두께의 확보, 표면마감성의 개선 및 색깔발현을 위해 혼합되는 것으로서, 석회석 분말, 중정석 분말, 티타늄화이트 (TiO2) 중 하나 또는 2 이상의 혼합에 의한 백색안료 48.9~69 중량%; 유색안료 0.1~10 중량 %;를 포함하여 구성된다.The pigment is mixed to ensure application thickness, improve surface finish, and express color. 48.9 to 69% by weight of white pigment obtained by mixing one or more of limestone powder, barite powder, and titanium white (TiO2); Contains 0.1 to 10% by weight of colored pigment.

유색안료는 카본블랙의 흑색안료와, 기타 적색, 녹색, 파란색, 노란색 등의 안료의 혼합에 의해 구성된다. Colored pigments are composed of a mixture of black pigments of carbon black and other pigments such as red, green, blue, and yellow.

본 발명에 의한 액상 폴리머 조성물은, 위 분체 조성물 100 중량부; 유기 폴리머 5~20 중량부; 물 15~35 중량부;를 포함하여 구성된다.The liquid polymer composition according to the present invention includes 100 parts by weight of the above powder composition; 5 to 20 parts by weight of organic polymer; It consists of 15 to 35 parts by weight of water.

유기 폴리머는 부착 및 내구성 개선을 위해 사용되며, 아크릴계, 스타이렌-아크릴계, 비닐아세테이트 에틸렌(VAE)계, 폴리비닐 아세테이트(PVA)계, 스타이렌-부타디엔 수지(SBR)계 폴리머 중 하나 또는 2 이상의 혼합에 의해 형성된다.Organic polymers are used to improve adhesion and durability, and are one or more of acrylic, styrene-acrylic, vinyl acetate ethylene (VAE), polyvinyl acetate (PVA), and styrene-butadiene resin (SBR) polymers. Formed by mixing.

상기 범위 미만이면 폴리머 첨가 효과가 미미하여 표면경도 및 내구성이 저하되고, 상기 범위를 초과하면 유기물에 의한 초기 수화반응 억제에 따른 물성발현이 어렵게 된다.If it is less than the above range, the effect of adding polymer is insignificant, resulting in a decrease in surface hardness and durability, and if it exceeds the above range, it becomes difficult to develop physical properties due to inhibition of the initial hydration reaction by organic substances.

본 발명은 이산화탄소 반응경화형 시멘트인 칼슘-실리케이트 시멘트 클링커 (CSC)를 활용한 것으로서, 내염성을 갖는 속경형 유무기 복합 코팅재 조성물로 사용될 수 있다.The present invention utilizes calcium-silicate cement clinker (CSC), a carbon dioxide reaction hardening cement, and can be used as a fast-curing organic-inorganic composite coating composition with salt resistance.

본 발명의 핵심은 속경성을 발현하는 주요 수화물인 에트린자이트를 수화반응 초기에 효과적으로 생성시키는 것(화학식 1)과, CSC시멘트가 공기중의 이산화탄소와 탄산화반응을 통하여 장기적인 결정성장에 의해 장기물성을 증진시키는 것(화학식 2)에 있다. The core of the present invention is to effectively generate ettringite, the main hydrate that exhibits rapid hardening, at the beginning of the hydration reaction (Formula 1), and to create long-term crystal growth through carbonation reaction with carbon dioxide in the air. The goal is to improve physical properties (Formula 2).

화학식 1은 에트린자이트(Ettringite)를 형성하는 반응식이다.Chemical formula 1 is the reaction formula for forming ettringite.

[화학식 1][Formula 1]

3CaO + Al2O3 + 3(CaSO4ㆍ2H2O) + 26H2O → 3CaOAl2O3ㆍ3CaSO4ㆍ32H2O3CaO + Al 2 O 3 + 3(CaSO 4ㆍ 2H 2 O) + 26H2O → 3CaO Al 2 O 3ㆍ 3CaSO 4ㆍ 32H 2 O

화학식 2는 CSC 시멘트의 탄산화 반응식이다.Chemical formula 2 is the carbonation reaction formula of CSC cement.

[화학식 2][Formula 2]

CaSiO2 + CO2 → CaCO3 + SiO2 CaSiO 2 + CO 2 → CaCO 3 + SiO 2

Ca3Si2O7 + CO2 → 3CaCO3 + 2SiO2 Ca 3 Si 2 O 7 + CO 2 → 3CaCO 3 + 2SiO 2

이하, 본 발명에 의한 조성물의 물성을 입증하기 위한 실험내용 및 결과에 관하여 설명한다.Hereinafter, the details and results of experiments to prove the physical properties of the composition according to the present invention will be described.

Figure 112022139259557-pat00001
Figure 112022139259557-pat00001

표 1은 본 발명의 실시예 1 내지 3과, 비교예 1의 성분 및 배합에 관한 표이다.Table 1 is a table of ingredients and formulations of Examples 1 to 3 and Comparative Example 1 of the present invention.

본 발명의 실시예 1 내지 3은 속경성 시멘트를 사용한 배합 중 CSC 함량을 다양하게 변화시킨 것으로서, CSC 함량이 증가할수록 반응성을 보상하기 위하여 속경성 결합재(CAC, CSA)의 배합조건을 변형하여 제시한 것이다.Examples 1 to 3 of the present invention vary the CSC content during mixing using fast-setting cement, and the mixing conditions of the fast-setting binder (CAC, CSA) are modified to compensate for the reactivity as the CSC content increases. It was done.

비교예는 속경성시멘트를 사용하지 않고, 무기질 결합재 전량을 CSC 시멘트로 사용한 것이다.In the comparative example, fast-hardening cement was not used, and all of the inorganic binder was used as CSC cement.

C%는 무기질 결합재(시멘트) 100 중량%를 기준으로 한 배합비를 나타낸 것이고, T%는 분체 조성물(분말) 100 중량%를 기준으로 한 배합비를 나타낸 것이다.C% represents the mixing ratio based on 100% by weight of the inorganic binder (cement), and T% represents the mixing ratio based on 100% by weight of the powder composition (powder).

실험은 상대습도 60%, 표준온도 20℃의 조건에서 진행하였다.The experiment was conducted under conditions of 60% relative humidity and standard temperature of 20°C.

Figure 112022139259557-pat00002
Figure 112022139259557-pat00002

표 2는 본 발명의 실시예 1 내지 3과, 비교예 1에 관하여, 각 재령에 따라 각종 물성을 실험한 결과를 나타낸 것이다.Table 2 shows the results of testing various physical properties at different ages for Examples 1 to 3 and Comparative Example 1 of the present invention.

본 발명의 실시예 1 내지 3과 같이 무기질 결합재 중 속경성 재료가 혼합된 코팅재의 경우에는 초기 반응이 잘 진행되어 물성 발현이 양호하나, 비교예 1과 같이 CSC를 전량 무기결합재로 사용한 경우에는 재령 28일에 이르기까지 물성이 제대로 발현되지 않는 것을 알 수 있다.In the case of a coating material mixed with a fast-hardening material among the inorganic binders, as in Examples 1 to 3 of the present invention, the initial reaction proceeds well and the physical properties are good, but when CSC is used entirely as an inorganic binder, as in Comparative Example 1, the lifespan is delayed. It can be seen that the physical properties are not properly expressed until the 28th day.

56일의 장기 재령에 있어서는, CSC가 많이 혼입된 배합일수록 장기물성의 발현이 크게 증가하는 것으로 나타났는데, 이는 CSC 시멘트가 장기적으로 공기 중의 이산화탄소와 탄산화 반응을 일으킴에 기인하는 것으로 추정된다. In the long-term aging of 56 days, the expression of long-term properties increased significantly as the mix contained more CSC. This is believed to be due to the long-term carbonation reaction of CSC cement with carbon dioxide in the air.

비교예 1의 경우 56일 재령에서 일부 장기물성의 발현이 진행되나, 속경성 결합재가 들어간 본 발명의 실시예에 비해 현저히 떨어짐을 알 수 있다.In the case of Comparative Example 1, some long-term properties were developed at 56 days of age, but it was found to be significantly inferior to the example of the present invention containing a fast-hardening binder.

본 발명에 의한 조성물은 이산화탄소와의 탄산화 반응에 의해 장기물성의 증대효과를 얻을 수 있으면서도, 속경성 재료의 혼입에 의해 초기 물성 발현 또한 우수하다는 특징을 갖는다.The composition according to the present invention has the characteristic of being able to obtain an effect of increasing long-term physical properties through a carbonation reaction with carbon dioxide, and also having excellent initial physical properties due to the incorporation of fast-hardening materials.

따라서 염해의 우려가 큰 지역(해안가)에 설치된 구조물의 노출면에 도포하여 보호 및 보수가 가능하도록 하는 내염성 코팅재로 사용될 수 있으며, 제설제에 의해 손상된 도로포장 구조물 등에 대하여도 효과적으로 사용될 수 있다.Therefore, it can be used as a salt-resistant coating to enable protection and repair by applying it to the exposed surfaces of structures installed in areas with a high risk of salt damage (coastals), and it can also be effectively used on road pavement structures damaged by snow removal agents.

이상은 본 발명에 의해 구현될 수 있는 바람직한 실시예의 일부에 관하여 설명한 것에 불과하므로, 주지된 바와 같이 본 발명의 범위는 위의 실시예에 한정되어 해석되어서는 안 될 것이며, 위에서 설명된 본 발명의 기술적 사상과 그 근본을 함께 하는 기술적 사상은 모두 본 발명의 범위에 포함된다고 할 것이다.Since the above is only a description of some of the preferred embodiments that can be implemented by the present invention, as is well known, the scope of the present invention should not be construed as limited to the above embodiments, and the scope of the present invention described above Both the technical idea and the technical idea underlying it will be said to be included in the scope of the present invention.

Claims (8)

무기질 결합재를 포함하는 분체 조성물로서,
상기 무기질 결합재는,
칼슘-실리케이트 시멘트 (CSC : Calcium Silicate Cement) 20~80 중량%;
C12A7계 칼슘-알루미네이트 시멘트 (CAC : Calcium Aluminate Cement) 9~40 중량%;
황산칼슘 (CS : Calcium Sulfate) 10~40 중량%;를 포함하고,
상기 분체 조성물은,
상기 무기질 결합재 20~50 중량%;
유동화제, 증점제, 소포제의 혼합에 의한 작업성 혼화제 0.3~1.5 중량%;
안료 49~79 중량%;를 포함하고,
상기 작업성 혼화제는,
나프탈렌계, 멜라민계 또는 폴리카르본산계인 상기 유동화제 0.1~0.5 중량%;
스타치계 또는 셀룰로오즈계인 상기 증점제 0.1~0.5 중량%;
글리콜계 또는 실리콘계인 상기 소포제 0.1~0.5 중량%;를 포함하고,
상기 안료는,
석회석 분말, 중정석 분말, 티타늄화이트 (TiO2) 중 하나 또는 2 이상의 혼합에 의한 백색안료 48.9~69 중량%;
유색안료 0.1~10 중량 %;를
포함하는 것을 특징으로 하는 분체 조성물.
A powder composition containing an inorganic binder,
The inorganic binder is,
Calcium-silicate cement (CSC) 20-80% by weight;
C 12 A 7 series calcium-aluminate cement (CAC: Calcium Aluminate Cement) 9 to 40% by weight;
Contains 10 to 40% by weight of calcium sulfate (CS: Calcium Sulfate),
The powder composition is,
20 to 50% by weight of the inorganic binder;
0.3 to 1.5% by weight of workability admixture by mixing a fluidizer, thickener, and anti-foaming agent;
Contains 49 to 79% by weight of pigment;
The workability admixture is,
0.1 to 0.5% by weight of the fluidizing agent, which is naphthalene-based, melamine-based, or polycarboxylic acid-based;
0.1 to 0.5% by weight of the starch-based or cellulose-based thickener;
Contains 0.1 to 0.5% by weight of the antifoaming agent, which is glycol-based or silicone-based,
The pigment is,
48.9 to 69% by weight of white pigment made by one or a mixture of two or more of limestone powder, barite powder, and titanium white (TiO2);
Colored pigment 0.1~10% by weight;
A powder composition comprising:
제1항에 있어서,
상기 무기질 결합재는,
칼슘-설퍼-알루미네이트 시멘트 (CSA : Calcium Sulfoaluminate) 0.1~20 중량%;를
더 포함하는 것을 특징으로 하는 분체 조성물.
According to paragraph 1,
The inorganic binder is,
Calcium-sulfur-aluminate cement (CSA: Calcium Sulfoaluminate) 0.1~20% by weight;
A powder composition further comprising:
제1항 또는 제2항에 있어서,
상기 무기질 결합재는,
상기 무기질 결합재 100 중량부를 기준으로,
개미산리튬 (Lithium formate), 염화리튬(Lithium chloride), 탄산리튬(Lithium Carbonate), 리튬염(Lithium Salt), 아질산칼슘(Calcium Nitrite), 개미산아민(Amine Formate) 중 하나 또는 2 이상의 혼합에 의한 촉진제 0.1~1.0 중량부;
글루콘산소다(Sodium Glucoante), 주석산 (Tartaric acid), 구연산 (Citric acid), 인산알루미늄(Aluminium Phosphate), 아세트산구리(Copper Acetate), 황산아연(Zinc Sulfate) 중 하나 또는 2 이상의 혼합에 의한 지연제 0.2~2.0 중량부;를
더 포함하는 것을 특징으로 하는 분체 조성물.
According to claim 1 or 2,
The inorganic binder is,
Based on 100 parts by weight of the inorganic binder,
An accelerator made of one or a mixture of two or more of Lithium formate, Lithium chloride, Lithium Carbonate, Lithium Salt, Calcium Nitrite, and Amine Formate 0.1 to 1.0 parts by weight;
Delay caused by one or a mixture of two or more of Sodium Glucoante, Tartaric acid, Citric acid, Aluminum Phosphate, Copper Acetate, and Zinc Sulfate. 0.2 to 2.0 parts by weight;
A powder composition further comprising:
삭제delete 삭제delete 삭제delete 제1항의 분체 조성물 100 중량부;
유기 폴리머 5~20 중량부;
물 15~35 중량부;를
포함하는 것을 특징으로 하는 액상 폴리머 조성물.
100 parts by weight of the powder composition of claim 1;
5 to 20 parts by weight of organic polymer;
15 to 35 parts by weight of water;
A liquid polymer composition comprising:
제7항에 있어서,
상기 유기 폴리머는,
아크릴계, 스타이렌-아크릴계, 비닐아세테이트 에틸렌(VAE)계, 폴리비닐 아세테이트(PVA)계, 스타이렌-부타디엔 수지(SBR)계 폴리머 중 하나 또는 2 이상의 혼합에 의해 형성된 것을 특징으로 하는 액상 폴리머 조성물.
In clause 7,
The organic polymer is,
A liquid polymer composition, characterized in that it is formed by one or a mixture of two or more of acrylic-based, styrene-acrylic-based, vinyl acetate ethylene (VAE)-based, polyvinyl acetate (PVA)-based, and styrene-butadiene resin (SBR)-based polymers.
KR1020220183328A 2022-12-23 2022-12-23 Inorganic binder and liquid-phase polymer composition KR102612264B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020220183328A KR102612264B1 (en) 2022-12-23 2022-12-23 Inorganic binder and liquid-phase polymer composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020220183328A KR102612264B1 (en) 2022-12-23 2022-12-23 Inorganic binder and liquid-phase polymer composition

Publications (1)

Publication Number Publication Date
KR102612264B1 true KR102612264B1 (en) 2023-12-12

Family

ID=89159523

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020220183328A KR102612264B1 (en) 2022-12-23 2022-12-23 Inorganic binder and liquid-phase polymer composition

Country Status (1)

Country Link
KR (1) KR102612264B1 (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010028551A (en) * 1999-09-21 2001-04-06 명호근 Matrix for the continuous fiber reinforced cement composites using ultra-super fine cement
JP2006131488A (en) * 2004-10-07 2006-05-25 Ube Ind Ltd Acid resistant grout composition
JP2009526198A (en) 2006-02-07 2009-07-16 シー. コンリー,ダグラス Production of cementitious ash products with reduced carbon emissions
KR100973497B1 (en) * 2010-05-12 2010-08-03 임펙트디엔씨 주식회사 Rapid setting cement composite, rapid setting mortar composite and repairing method of concrete structure using the composite
JP5059285B2 (en) 2001-10-23 2012-10-24 電気化学工業株式会社 Cement admixture, cement composition, and cement concrete using the same
KR101877528B1 (en) * 2017-07-17 2018-07-11 동일씨엠 주식회사 Cement composition having rapid hardening properties for runway reparing and runway repairing method using the same
KR102066376B1 (en) * 2019-08-22 2020-01-15 김상훈 Eco-friendly colored concrete composition resistant to seawater and colored blocks for crashing waves manufactured by the same
JP2021175701A (en) 2020-04-24 2021-11-04 清水建設株式会社 Method for producing cement-containing molded body, and cement-containing molded body
JP2021187721A (en) 2020-06-04 2021-12-13 三菱マテリアル株式会社 Utilization method of co2 in cement manufacture exhaust gas and co2 utilization system
JP2022044570A (en) 2020-09-07 2022-03-17 太平洋セメント株式会社 Cement production method, cement production system, and cement hardened material production method
KR20220097663A (en) 2020-12-30 2022-07-08 한국석회석신소재연구재단 Manufacturing Method of Calcium Silicated Base Cement Clinker And Calcium Silicated Base Cement Clinker Hardening Body
JP2022156478A (en) * 2021-03-31 2022-10-14 住友大阪セメント株式会社 Cement composition and method for producing cement composition

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010028551A (en) * 1999-09-21 2001-04-06 명호근 Matrix for the continuous fiber reinforced cement composites using ultra-super fine cement
JP5059285B2 (en) 2001-10-23 2012-10-24 電気化学工業株式会社 Cement admixture, cement composition, and cement concrete using the same
JP2006131488A (en) * 2004-10-07 2006-05-25 Ube Ind Ltd Acid resistant grout composition
JP2009526198A (en) 2006-02-07 2009-07-16 シー. コンリー,ダグラス Production of cementitious ash products with reduced carbon emissions
KR100973497B1 (en) * 2010-05-12 2010-08-03 임펙트디엔씨 주식회사 Rapid setting cement composite, rapid setting mortar composite and repairing method of concrete structure using the composite
KR101877528B1 (en) * 2017-07-17 2018-07-11 동일씨엠 주식회사 Cement composition having rapid hardening properties for runway reparing and runway repairing method using the same
KR102066376B1 (en) * 2019-08-22 2020-01-15 김상훈 Eco-friendly colored concrete composition resistant to seawater and colored blocks for crashing waves manufactured by the same
JP2021175701A (en) 2020-04-24 2021-11-04 清水建設株式会社 Method for producing cement-containing molded body, and cement-containing molded body
JP2021187721A (en) 2020-06-04 2021-12-13 三菱マテリアル株式会社 Utilization method of co2 in cement manufacture exhaust gas and co2 utilization system
JP2022044570A (en) 2020-09-07 2022-03-17 太平洋セメント株式会社 Cement production method, cement production system, and cement hardened material production method
KR20220097663A (en) 2020-12-30 2022-07-08 한국석회석신소재연구재단 Manufacturing Method of Calcium Silicated Base Cement Clinker And Calcium Silicated Base Cement Clinker Hardening Body
JP2022156478A (en) * 2021-03-31 2022-10-14 住友大阪セメント株式会社 Cement composition and method for producing cement composition

Similar Documents

Publication Publication Date Title
EP1274664B1 (en) Non-efflorescing cementitious bodies
JP3487133B2 (en) Ultra-fast hardening non-shrink grout material
KR100670924B1 (en) Composition of polymer cement paste and road pavement using the same
KR100835702B1 (en) Waterproof admixture for concrete having a corrosion inhibition function
KR101900248B1 (en) Improved cement mortar composition with anti-environment performance
JP2006131488A (en) Acid resistant grout composition
AU2015239675A1 (en) Quick-drying building material composition based on a mineral hybrid binder
KR100971226B1 (en) Cement mixture for chloride resistance in road pavement and repair
KR101565119B1 (en) Cement Mortar Composite with Water Resistance for Road and Bridge Surface
KR100311286B1 (en) Hydraulic inorganic coating composition
KR100831591B1 (en) A composition for fast setting and hydraulic ceramic based overlay
KR101046970B1 (en) Finishing composition using ladle slag crystal growth reaction as surface protection material of concrete structure
KR101318935B1 (en) Inorganic material for mending a crack repair of concrete structures
KR101976650B1 (en) Rapid setting mortar composition using distributing crushed stone and rapid setting concrete composition using the same
KR102612264B1 (en) Inorganic binder and liquid-phase polymer composition
US5401310A (en) Additive composition with insulating, impermeabilizing and antishrink properties
JP2021119115A (en) Quick-hardening polymer cement composition and quick-hardening polymer cement mortar
KR101500958B1 (en) Ultra rapid hardening polymer modified concrete repairing material
JPH07315907A (en) Polymer cement based composite material
KR101933677B1 (en) Concrete repair materials for improved durability of concrete structure, and method for repairing concrete structure using this same
AU2022418817A1 (en) Quick-drying levelling compound for decorative floor coverings
JP2024501295A (en) Three-component hydraulic binder composition
JP2000160057A (en) Material for building and civil engineering work
KR100404330B1 (en) The compound of blast furnace slag-white cement unused clinker
KR101086851B1 (en) Waterproof material composition and manufacture of same

Legal Events

Date Code Title Description
E701 Decision to grant or registration of patent right
GRNT Written decision to grant